Techniques for use of nanotechnology in photovoltaics

ABSTRACT

Techniques for combining nanotechnology with photovoltaics are provided. In one aspect, a method of forming a photovoltaic device is provided comprising the following steps. A plurality of nanowires are formed on a substrate, wherein the plurality of nanowires attached to the substrate comprises a nanowire forest. In the presence of a first doping agent and a first volatile precursor, a first doped semiconductor layer is conformally deposited over the nanowire forest. In the presence of a second doping agent and a second volatile precursor, a second doped semiconductor layer is conformally deposited over the first doped layer. The first doping agent comprises one of an n-type doping agent and a p-type doping agent and the second doping agent comprises a different one of the n-type doping agent and the p-type doping agent from the first doping agent. A transparent electrode layer is deposited over the second doped semiconductor layer.

STATEMENT OF GOVERNMENT RIGHTS

This invention was made with Government support under N66001-05-C-8043awarded by Defense Advanced Research Projects Agency (DARPA). TheGovernment has certain rights in this invention.

FIELD OF THE INVENTION

The present invention relates to use of nanotechnology in photovoltaics,and more particularly, to nanostructure-based photovoltaic devices.

BACKGROUND OF THE INVENTION

Photovoltaic devices, such as photocells, are an important energy sourcethat has thus far remained underutilized for widespread energyproduction due to undesirable efficiency and/or production cost factors.For example, conventional photocells comprise a silicon-based substratethat includes a large-area p-n junction. Crystalline semiconductorsubstrates, such as silicon, are expensive, making production ofphotocells cost prohibitive for many applications. Further, photocellsgenerate electrical energy by converting photons from a light sourceinto electricity (e.g., by freeing electron-hole pairs). Conventionalphotocells typically provide a light-to-electricity conversionefficiency of only up to about 25%. This low conversion efficiencysimilarly makes photocells an undesirable option for many applications.

Attempts have been made to increase photocell energy conversionefficiency. Some of the attempts have employed nanotechnology as a tool.See, for example, U.S. Patent Application No. 2005/0009224 filed by Yanget al., entitled “Nanowire Array and Nanowire Solar Cells and Methodsfor Forming the Same” (wherein nanowire oxides are used in conjunctionwith a charge transport medium in optoelectronic devices); U.S. PatentApplication No. 2005/0214967 filed by Scher et al., entitled“Nanostructure and Nanocomposite Based Compositions and PhotovoltaicDevices” (wherein nanostructures, such as core-shell nanocrystals, areused in photovoltaic devices oriented horizontally along the plane ofthe electrodes); and Kayes et al., Comparison of the Device PhysicsPrinciples of Planar and Radial p-n Junction Nanorod Solar Cells, 97 J.APPL. PHYS. 114302 (2005) (wherein radial p-n junction nanorod solarcells are described).

As these references show, nanotechnology can be employed inphotovoltaics. However, improved techniques for combining thesetechnologies to cost-effectively produce more efficient photovoltaicdevices are needed.

SUMMARY OF THE INVENTION

The present invention provides techniques for combining nanotechnologywith photovoltaics. In one aspect of the invention, a method of forminga photovoltaic device is provided comprising the following steps. Aplurality of nanowires are formed on a substrate, wherein the pluralityof nanowires attached to the substrate comprises a nanowire forest. Inthe presence of a first doping agent and a first volatile precursor, afirst doped semiconductor layer is conformally deposited over at least aportion of the nanowire forest. In the presence of a second doping agentand a second volatile precursor, a second doped semiconductor layer isconformally deposited over at least a portion of the first doped layer.The first doping agent comprises one of an n-type doping agent and ap-type doping agent and the second doping agent comprises a differentone of the n-type doping agent and the p-type doping agent from thefirst doping agent. A transparent electrode layer is deposited over atleast a portion of the second doped semiconductor layer.

In another aspect of the invention, a method of forming a photovoltaicdevice is provided comprising the following steps. In the presence of afirst doping agent and a first volatile precursor, a plurality ofnanowires are formed on a substrate, wherein the plurality of nanowiresattached to the substrate comprises a nanowire forest. In the presenceof a second doping agent and a second volatile precursor, a dopedsemiconductor layer is conformally deposited over at least a portion ofthe nanowire forest. The first doping agent comprises one of an n-typedoping agent and a p-type doping agent and the second doping agentcomprises a different one of the n-type doping agent and the p-typedoping agent from the first doping agent. A transparent electrode layeris deposited over at least a portion of the doped semiconductor layer.

In yet another aspect of the invention, a photovoltaic device isprovided. The photovoltaic device comprises a substrate; a plurality ofnanowires on the substrate, wherein the plurality of nanowires attachedto the substrate comprises a nanowire forest; a first dopedsemiconductor layer disposed conformally over at least a portion of thenanowire forest, the first doped semiconductor layer comprising a firstdoping agent; a second doped semiconductor layer disposed conformallyover at least a portion of the first doped semiconductor layer, thesecond doped semiconductor layer comprising a second doping agent,wherein the first doping agent comprises one of an n-type doping agentand a p-type doping agent and the second doping agent comprises adifferent one of the n-type doping agent and the p-type doping agentfrom the first doping agent; and a transparent electrode layer disposedover at least a portion of the second doped semiconductor layer.

In still another aspect of the invention, a photovoltaic device isprovided. The photovoltaic device comprises a substrate; a plurality ofnanowires on the substrate, the nanowires comprising a first dopingagent and wherein the plurality of nanowires attached to the substratecomprises a nanowire forest; a doped semiconductor layer disposedconformally over at least a portion of the nanowire forest, the dopedsemiconductor layer comprising a second doping agent, wherein the firstdoping agent comprises one of an n-type doping agent and a p-type dopingagent and the second doping agent comprises a different one of then-type doping agent and the p-type doping agent from the first dopingagent; and a transparent electrode layer disposed over at least aportion of the doped semiconductor layer.

A more complete understanding of the present invention, as well asfurther features and advantages of the present invention, will beobtained by reference to the following detailed description anddrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram illustrating an exemplary methodology for growing ananowire forest according to an embodiment of the present invention;

FIG. 2 is a scanning electron micrograph image of an exemplary nanowireforest according to an embodiment of the present invention;

FIG. 3 is a diagram illustrating an exemplary methodology for forming aphotovoltaic device according to an embodiment of the present invention;

FIG. 4 is a diagram illustrating another exemplary methodology forforming a photovoltaic device according to an embodiment of the presentinvention; and

FIG. 5 is a diagram illustrating an exemplary photocell according to anembodiment of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

FIG. 1 is a diagram illustrating exemplary methodology 100 for growing ananowire forest. The term “nanowire forest,” as used herein, refers to aplurality of nanowires attached to a substrate. As will be described indetail below, the growth of the nanowire forest is conducted in achemical vapor environment.

Nanowires are highly-anisotropic, rod-like crystals with diameters d ofbetween about ten nanometers (nm) and about 70 nm and lengths L ofbetween about 0.1 micrometers (μm) and about 100 μm. Due to thenanowires having large L to d ratios, the surface area of the substrateis increased by a factor (4 L/d)f wherein f denotes the fraction of thesubstrate area covered by nanowires. By way of example only, for a fivepercent substrate areal coverage, nanowires of diameter d=40 nm andlength L=five μm will provide a surface area that is 25 times greaterthan that of the substrate alone.

While the present description is directed to nanowires being a preferrednanostructure for use herein, any other suitable nanostructures may besimilarly employed. Other suitable nanostructures include, but are notlimited to, nanoparticles, quantum dots and other nanoscale materials.

In step 102 of FIG. 1, at least a portion of substrate 110 is coatedwith a catalyst metal to form catalyst layer (film) 112. Catalyst layer112 can be deposited on substrate 110 using chemical vapor deposition(CVD) techniques.

Substrate 110 can comprise any suitable substrate material, including,but not limited to, one or more of glass, quartz and a semiconductormaterial, such as silicon (Si) or germanium (Ge). Optionally, whensubstrate 110 comprises a semiconductor material, substrate 110 can bedoped with either an n-type or a p-type doping agent, so as to beconductive. Suitable doping agents include, but are not limited to,diborane (B₂H₆) (a p-type doping agent) and phosphine (PH₃) (an n-typedoping agent). According to an exemplary embodiment, substrate 110comprises Si and is doped with an n-type doping agent.

Catalyst layer 112 deposited onto substrate 110, can comprise anysuitable catalyst metal, including, but not limited to, one or more ofgold (Au), gallium (Ga) and indium (In). According to one exemplaryembodiment, catalyst layer 112 comprises Au and is deposited onsubstrate 110 to a thickness of up to about ten Angstroms (Å).

In step 104, substrate 110 is annealed to cause catalyst layer 112 toform small droplets 114. According to an exemplary embodiment, substrate110 is annealed at a temperature of between about 400 degrees Celsius (°C.) and about 500° C. to form droplets 114 having diameters of betweenabout ten nm and about 30 nm. Further, as shown in FIG. 1, droplets 114of varying diameters are typically formed by the annealing process.

In step 106, substrate 110 is exposed to an ambient of one or morevolatile precursors 116. Suitable precursors include, but are notlimited to, one or more of silane (SiH₄) and germane (GeH₄). Thespecific precursor used will dictate the nanowire composition. Forexample, if SiH₄ is employed as the precursor, then Si nanowire growth(as described in step 108, below) will result. Similarly, if GeH₄ isemployed as the precursor, then Ge nanowire growth (as described in step108, below) will result. A combination of SiH₄ and GeH₄ will result inSiGe nanowire growth, wherein the relative concentration of Si and Gewill depend on the ratio of partial pressures of SiH₄ and GeH₄ in thegrowth ambient, as well as, on the growth temperature. Suitable partialpressures of the precursor(s) and temperature parameters are providedbelow.

By way of example only, suitable growth conditions for Si nanowiresinclude a temperature of between about 400° C. and about 500° C. and apartial pressure of the precursor of between about 0.1 torr and about100 torr. Suitable growth conditions for Ge nanowires include atemperature of between about 250° C. and about 300° C. and a partialpressure of the precursor of between about 0.1 torr and about 100 torr.

Optionally, an n-type and/or a p-type doping agent may be introduced tothe ambient during nanowire growth. For example, some embodiments,described below, include n-type and/or p-type doped nanowires. Suitabledoping agents include, but are not limited to, B₂H₆ and PH₃. By way ofexample only, if substrate 110 is exposed to an ambient of GeH₄ andB₂H₆, boron-doped (B-doped), p-type Ge nanowire growth will result.Similarly, if substrate 110 is exposed to an ambient of GeH₄ and PH₃,phosphorous-doped (P-doped), n-type Ge nanowire growth will result.

In step 108, droplets 114 will mediate CVD growth of crystals, namelynanowires 118. According to an exemplary embodiment, when droplets 114comprise Au as the catalyst metal, and the growth conditions outlinedabove are employed, highly anisotropic Si or Ge nanowires are produced.

The diameters of the nanowires produced are determined by the diameters(i.e., sizes) of the respective droplets 114. The lengths of thenanowires produced are determined by the growth time and growthpressure. For example, at a partial pressure of GeH₄ in the CVD reactorof 0.5 torr and a temperature of 285° C., the longitudinal growth ratefor Ge nanowires is about five μm/hour. At constant temperature, e.g.,285° C., the nanowire growth rate depends linearly on the partialpressure of GeH₄ in the growth ambient. At constant pressure, the growthrate depends exponentially on the temperature (i.e., in a limitedtemperature window, because at higher temperatures the nanowire growthcan be complicated by conformal growth).

As described above, the nanowires produced can have diameters of betweenabout ten nm and about 70 nm and lengths of between about 0.1 μm andabout 100 μm. For example, the nanowires produced can have diameters ofbetween about 20 nm and about 50 nm and lengths of between about one μmand about ten μm.

FIG. 2 is scanning electron micrograph image 200 of exemplary nanowireforest 202, e.g., produced according to methodology 100, described inconjunction with the description of FIG. 1, above. Nanowire forest 202comprises Ge nanowires grown predominately in a vertical direction. Thesubstrate employed is an n-type doped Si wafer.

As will be described in detail below, the nanowire forests posses a veryhigh absorption coefficient of incident, visible electromagnetic waves(light). According to the present techniques, these highlight-absorptive properties can be utilized by incorporating thenanowire forests into photovoltaic devices, such as photocells, toconvert light into electricity with enhanced efficiency and to reducethe overall size of the devices to minimize use of costly productionmaterials.

FIG. 3 is a diagram illustrating exemplary methodology 300 for forming aphotovoltaic device. As will be described in detail below, thephotovoltaic device is formed using CVD growth techniques.

In step 302, the starting structure for the photocell is a nanowireforest formed in accordance with exemplary methodology 100, describedabove, and comprises nanowires 301 on substrate 303. Substrate 303comprises a semiconductor material doped with a doping agent, so as tobe conductive. The doping of a semiconductor substrate material isdescribed, for example, in conjunction with the description of FIG. 1,above.

According to one exemplary embodiment, substrate 303 comprises an n-typedoped Si wafer and nanowires 301 comprise Ge. The use of Ge nanowires,in particular, significantly decreases reflectivity (e.g., to below 10⁻⁴across the whole visible light spectrum), i.e., rendering the nanowireforest a black body, and thus enhances the desirable light absorptiveproperties of the nanowire forest.

In step 304, doped semiconductor layer 310, which may comprise either ap-type or an n-type doped layer, is formed over the nanowire forest byconformal CVD growth (so as to have the same relative shape as theunderlying structure, i.e., the nanowire forest). According to oneexemplary embodiment, wherein doped semiconductor layer 310 comprises ap-type doped layer, doped semiconductor layer 310 is formed by exposingthe nanowire forest to an ambient of GeH₄ and B₂H₆. This results inB-doped, p-type Ge layer growth. At a temperature of about 350° C., aGeH₄ partial pressure of about 0.33 torr and a B₂H₆/GeH₄ ratio of about0.0001, the growth rate of a p-type doped semiconductor layer 310 willbe on the order of about 200 nm/hour, with a doping concentration ofabout 10¹⁸ cm⁻³.

According to another exemplary embodiment, wherein doped semiconductorlayer 310 comprises an n-type doped layer, doped semiconductor layer 310is formed by exposing the nanowire forest to an ambient of GeH₄ and PH₃.This results in P-doped, n-type Ge layer growth. At a temperature ofabout 350° C., a GeH₄ partial pressure of about 0.33 torr and a PH₃/GeH₄ratio of about 0.0001, the growth rate of an n-type doped semiconductorlayer 310 will be on the order of about 210 nm/hour, with a dopingconcentration of about 10¹⁸ cm⁻³. The growth rates and dopingconcentrations given can vary based on temperature and gas flow ratios,and therefore are merely exemplary.

In step 306, doped semiconductor layer 312, which may comprise either ap-type or an n-type doped layer, is formed over doped semiconductorlayer 310 by conformal CVD growth. The doping of doped semiconductorlayer 310 has to be different from the doping of doped semiconductorlayer 312. Namely, if doped semiconductor layer 310 comprises a p-typedoped layer, then doped semiconductor layer 312 must comprise an n-typedoped layer. Similarly, if doped semiconductor layer 310 comprises ann-type doped layer, then doped semiconductor layer 312 must comprise ap-type doped layer.

According to one exemplary embodiment, wherein doped semiconductor layer312 comprises a p-type doped layer, doped semiconductor layer 312 isformed by exposing the nanowire forest/doped semiconductor layer 310structure to an ambient of GeH₄ and B₂H₆. As described above, thisresults in B-doped, p-type Ge layer growth. At a temperature of about350° C., a GeH₄ partial pressure of about 0.33 torr and a B₂H₆/GeH₄ratio of about 0.0001, the growth rate of a p-type doped semiconductorlayer 312 will be on the order of about 200 nm/hour, with a dopingconcentration of about 10¹⁸ cm⁻³.

According to another exemplary embodiment, wherein doped semiconductorlayer 312 comprises an n-type doped layer, doped semiconductor layer 312is formed by exposing the nanowire forest/doped semiconductor layer 310structure to an ambient of GeH₄ and PH₃. As described above, thisresults in P-doped, n-type Ge layer growth. At a temperature of about350° C., a GeH₄ partial pressure of about 0.33 torr and a PH₃/GeH₄ ratioof about 0.0001, the growth rate of n-type doped semiconductor layer 312will be on the order of about 210 nm/hour, with a doping concentrationof about 10¹⁸ cm⁻³. The growth rate and doping concentration given canvary based on temperature and gas flow ratios, and therefore are merelyexemplary.

In step 308, the nanowire forest/doped semiconductor layer 310/dopedsemiconductor layer 312 structure is capped with transparent electrodelayer 314. Transparent electrode layer 314 may be disposed using CVD.According to an exemplary embodiment, transparent electrode layer 314comprises indium tin oxide (ITO).

As a result of methodology 300, a p-n junction is formed over thenanowire forest. As will be described, for example, in conjunction withthe description of FIG. 5, below, the resulting structure can be used asa photocell.

FIG. 4 is a diagram illustrating exemplary methodology 400 for forming aphotovoltaic device. As will be described in detail below, thephotovoltaic device is formed using CVD growth techniques.

In step 402, the starting structure for the photovoltaic device is ananowire forest formed in accordance with exemplary methodology 100,described above, and comprises nanowires 401 on substrate 403. Substrate403 comprises a semiconductor material and is doped with a doping agent,so as to be conductive. The doping of a semiconductor substrate materialis described, for example, in conjunction with the description of FIG.1, above. According to one exemplary embodiment, substrate 403 comprisesan n-type doped Si wafer.

Nanowires 401 are doped with either a p-type or an n-type doping agentand thus are conductive. Namely, nanowires 401 may comprise eitherp-type or n-type doped nanowires. According to one exemplary embodiment,nanowires 401 comprise p-type or n-type doped Ge nanowires. The dopingof nanowires is described, for example, in conjunction with thedescription of FIG. 1, above.

In step 404, doped semiconductor layer 410, which may comprise either ap-type or an n-type doped layer, is formed over the nanowire forest byconformal CVD growth (so as to have the same relative shape as theunderlying structure, i.e., the nanowire forest). The doping of dopedsemiconductor layer 410 has to be different from the doping of nanowires401. Namely, if nanowires 401 comprise p-type doped nanowires, thendoped semiconductor layer 410 must comprise an n-type doped layer.Similarly, if nanowires 401 comprise n-type doped nanowires, then dopedsemiconductor layer 410 must comprise a p-type doped layer.

According to one exemplary embodiment, wherein doped semiconductor layer410 comprises a p-type doped layer, doped semiconductor layer 410 isformed by exposing the nanowire forest to an ambient of GeH₄ and B₂H₆.This results in B-doped, p-type Ge layer growth. At a temperature ofabout 350° C., a GeH₄ partial pressure of about 0.33 torr and aB₂H₆/GeH₄ ratio of about 0.0001, the growth rate of a p-type dopedsemiconductor layer 410 will be on the order of about 200 nm/hour, witha doping concentration of about 10¹⁸ cm⁻³.

According to another exemplary embodiment, wherein doped semiconductorlayer 410 comprises an n-type doped layer, doped semiconductor layer 410is formed by exposing the nanowire forest to an ambient of GeH₄ and PH₃.This results in P-doped, n-type Ge layer growth. At a temperature ofabout 350° C., a GeH₄ partial pressure of about 0.33 torr and a PH₃/GeH₄ratio of about 0.0001, the growth rate of an n-type doped semiconductorlayer 410 will be on the order of about 210 nm/hour, with a dopingconcentration of about 10¹⁸ cm⁻³. The growth rates and dopingconcentrations given can vary based on temperature and gas flow ratios,and therefore are merely exemplary.

In step 406, the nanowire forest/doped semiconductor layer 410 structureis capped with transparent electrode layer 414. Transparent electrodelayer 414 may be disposed using CVD. According to an exemplaryembodiment, transparent electrode layer 414 comprises ITO.

As a result of methodology 400, a p-n junction is formed with the dopednanowires. As will be described, for example, in conjunction with thedescription of FIG. 5, below, the resulting structure can be used as aphotocell.

FIG. 5 is a diagram illustrating exemplary photocell 502. Photocell 502comprises, e.g., n-type, doped substrate 504, nanowire-based p-njunctions 506 and transparent electrode layer 508. The use ofnanowire-based p-n junctions in a photocell increases the surface areaof the p-n junctions, which is beneficial in enhancing light absorption.

Further, the use of nanowire-based p-n junctions in a photocell takesadvantage of the single crystal structure of a nanowire. Namely, theperformance of a photocell can be degraded if the underlying materialhas defects. For example, grain boundaries enhance minority carrierrecombination, thus reducing carrier lifetime and increasing the darkcurrent. The grain boundaries also reduce majority carrier mobility andincrease the series resistance of the photocell. See, for example, H. C.Card et al., Electronic Processes At Grain Boundaries in PolycrystallineSemiconductors Under Optical Illumination, IEEE TRANS. ELECTRON DEVICESED-24, 397-402 (1977), the disclosure of which is incorporated byreference herein. As such, single crystal structures, such as nanowires,can minimize or eliminate the presence of material defects and thedecrease in performance associated therewith.

Photocell 502 may be fabricated using either methodology 300 ormethodology 400 described, for example, in conjunction with thedescription of FIGS. 3 and 4, respectively, above. Thus, for example, ifphotocell 502 is fabricated using methodology 300, then nanowire-basedp-n junctions 506 comprise two doped semiconductor layers formed, i.e.,disposed conformally, over a nanowire forest. Similarly, if photocell502 is fabricated using methodology 400, then nanowire-based p-njunctions 506 comprise a single doped semiconductor layer formed, i.e.,disposed conformally, over a doped nanowire forest.

One of the challenges in photovoltaic device, i.e., photocell,applications is to maximize solar light absorption. The design ofphotocell 502 incorporating a plurality of nanowire-based p-n junctionsis based on the discovery that a plurality of nanowires enables veryhigh light absorption. Specifically, the absorption spectrum of variousfilms of Ge nanowires have been measured, and showed 99 percentabsorption over most of the relevant spectral range.

Photocell 502 can be configured to optimize the absorption of incominglight. One way to achieve this is by employing an irregularconfiguration of nanowire-based p-n junctions 506. Such an irregularconfiguration is shown in FIG. 5, wherein some of nanowire-based p-njunctions 506 are oriented perpendicular to substrate 504, e.g., at anangle θ₁ between about 75 degrees to about 90 degrees relative tosubstrate 504, and others of nanowire-based p-n junctions 506 areoriented nearly parallel to substrate 504, e.g., at an angle θ₂ up toabout 45 degrees relative to substrate 504.

This irregular configuration helps optimize the orientations ofnanowire-based p-n junctions 506 with respect to the angles of incominglight. For example, the nanowire-based p-n junctions 506 oriented nearlyparallel to substrate 504 enhance absorption by aligning with theelectric field vectors of the incoming light.

An irregular nanowire configuration can be produced using either anon-crystalline substrate, or a crystalline substrate with a rough,faceted surface (i.e., a crystalline Si substrate with a rough, facetedsurface). A certain degree of irregularity is typically observed due tothe ubiquitous imperfections of the substrate surface. However,according to an exemplary embodiment, the substrate surface isintentionally roughened or rendered non-crystalline (for example, by iontreatment) to increase irregular nanowire growth. Preferably, thespatial wavelengths of the surface roughness are smaller than thewavelength of the absorbed light (the wavelengths of absorbed light canbe, e.g., between about 400 nm and about 800 nm).

Further, while most of the enhanced light absorption is caused by“roughness” of the nanowire film (see, for example, H. Kaplan, BlackCoatings Are Critical In Optical Design, 31 PHOTON. SPECTRA 48-50 (1997)and C. Amra, From Light Scattering to the Microstructure of Thin FilmMultilayers, 32 APPL. OPT. 5481-5491 (1993), the disclosures of whichare incorporated by reference herein) a plurality of nanowires also showaltered absorption/reflection properties due to coupling between thenanowires, which is not found with individual nanowires.

These coupling modes can be further exploited for optimum lightabsorption. For example, the optical properties of a plurality ofnanowires (or clusters of nanowires) can be governed by dipole-dipoleinteractions. For example, the individual nanowires can interact as“quasi-antennas” with the incident electrical field. The radiation fieldfrom these antennas will interact with other nanowires, thus alteringthe collective optical properties of the nanowire film. Further, thewavefunction of nanowires can overlap (couple quantum mechanically),which will alter the optical properties of nanowire films. In addition,the dielectric constants can be a function of the size, e.g., lengthand/or diameter, of the nanowire.

Although illustrative embodiments of the present invention have beendescribed herein, it is to be understood that the invention is notlimited to those precise embodiments, and that various other changes andmodifications may be made by one skilled in the art without departingfrom the scope of the invention.

1. A method of forming a photovoltaic device, the method comprising thesteps of: forming a plurality of silicon, germanium or silicon germaniumnanowires on a substrate, wherein the plurality of nanowires attached tothe substrate comprises a nanowire forest; in the presence of a firstdoping agent and a first volatile precursor, depositing a first dopedsemiconductor layer over the nanowire forest that conforms to, and hasthe same relative shape as, the nanowire forest; in the presence of asecond doping agent and a second volatile precursor, depositing a seconddoped semiconductor layer on the first doped semiconductor layer thatconforms to, and has the same relative shape as, the nanowire forest,wherein at least one of the first volatile precursor and the secondvolatile precursor comprises one or more of silane and germane, andwherein the first doping agent comprises one of an n-type doping agentand a p-type doping agent and the second doping agent comprises adifferent one of the n-type doping agent and the p-type doping agentfrom the first doping agent, such that a p-n junction is formed over thenanowire forest; and depositing a transparent electrode layer over atleast a portion of the second doped semiconductor layer.
 2. The methodof claim 1, wherein the forming step further comprises the step of:doping the substrate with an n-type doping agent.
 3. The method of claim1, wherein the forming step further comprises the steps of: depositingat least one catalyst metal layer on the substrate; annealing thesubstrate; exposing the substrate to at least one nanowire volatileprecursor; and growing the plurality of nanowires.
 4. The method ofclaim 3, wherein the at least one catalyst metal layer comprises one ormore of gold, gallium and indium.
 5. The method of claim 3, wherein theat least one nanowire volatile precursor comprises one or more of silaneand germane.
 6. The method of claim 3, wherein the substrate is annealedat a temperature of between about 400° C. and about 500° C.
 7. Themethod of claim 1, wherein the n-type doping agent comprises phosphineand the p-type doping agent comprises diborane.
 8. (canceled)
 9. Themethod of claim 1, wherein one or more of the first doped layer, thesecond doped layer and the transparent electrode layer are deposited bychemical vapor deposition.
 10. The method of claim 1, further comprisingthe step of: roughening at least a portion of a surface of the substrateonto which the plurality of nanowires are formed.
 11. A method offorming a photovoltaic device, the method comprising the steps of: inthe presence of a first doping agent and a first volatile precursor,forming a plurality of doped nanowires on a substrate to form a nanowireforest; in the presence of a second doping agent and a second volatileprecursor, depositing a doped semiconductor layer on the nanowire forestthat conforms to, and has the same relative shape as, the nanowireforest; and depositing a transparent electrode layer over at least aportion of the doped semiconductor layer, wherein the first volatileprecursor and the second volatile precursor each comprises germane, andwherein the first doping agent comprises one of an n-type doping agentand a p-type doping agent and the second doping agent comprises adifferent one of the n-type doping agent and the p-type doping agentfrom the first doping agent, such that a p-n junction is formed with thedoped nanowires.
 12. (canceled)
 13. (canceled)
 14. (canceled) 15.(canceled)
 16. (canceled)
 17. (canceled)
 18. (canceled)
 19. (canceled)20. (canceled)
 21. The method of claim 11, wherein the forming stepfurther comprises the step of: doping the substrate with an n-typedoping agent.
 22. The method of claim 11, wherein the forming stepfurther comprises the steps of: depositing at least one catalyst metallayer on the substrate; annealing the substrate; exposing the substrateto at least one nanowire volatile precursor; and growing the pluralityof nanowires.
 23. The method of claim 22, wherein the at least onecatalyst metal layer comprises one or more of gold, gallium and indium.24. The method of claim 22, wherein the substrate is annealed at atemperature of between about 400° C. and about 500° C.
 25. The method ofclaim 11, wherein the n-type doping agent comprises phosphine and thep-type doping agent comprises diborane.
 26. (canceled)
 27. The method ofclaim 11, wherein one or more of the doped semiconductor layer and thetransparent electrode layer are deposited by chemical vapor deposition.28. The method of claim 11, further comprising the step of: rougheningat least a portion of a surface of the substrate onto which theplurality of nanowires are formed.